Anthraquinone vat dyestuffs of the phthaloylacridone series



3,164,592 Patented Jan. 5, 1965 United States Patent Ofiice 4 Claims.(31. 260-249 The present invention provides valuable blue anthraquinonevat dyestufis of the formula can be further condensed with theaminotrifluoromethylbenzene, or 1 mol of cyanuric chloride canadvantageously be condensed first with 1 mol of theaminotrifluoromethylbenzene to form the condensation product of theformula I NHR which product can then be condensed with 2 mols of2-amino-3:4-phthaloylacridone to formthe'finished dyestufI.

The 2-amino-3:4-phthaloylacridone to be used as starting materials inthe process of the invention can contain further substituents, forexample, halogen atoms, in the acridone or phthaloyl radical. Asexamples the unsubstituted 2-amino-3:4-phthaloylacridone, and 2-amino-7-chloro-3:4-phthaloylacridone may be mentioned.

The aminotrifluorobenzene to be used in the process of the inventioncontain one or two trifluoromethyl'groups in the benzene radical, whichlatter can also be substituted by halogen atoms. Compounds of theformula in which X represents chlorine or hydrogen, and representstrifluoromethyl or hydrogen are advantageously used.

'As examples, there may be named 1-arnino-3-trifluoromethylbenzene,1-amino-3:S-di-(trifiuoromethyl)-benzene and1-amino-2-chloro-5-trifiuoromethylbenzene.

The reaction is advantageously carried out in a solvent or diluent. Forthe preparation of the compound of the Formula 3 the condensation isadvantageously carried out I in an aqueous medium in the cold, in whichprocess it is of advantage to add to the water an inert solvent that ismiscible with water, for example, acetone or dioxane, and also an agentcapable of binding acid such as sodium carbonate or sodium acetate. Thefurther condensation of the compound of the Formula 3 with the2-amino-3:4- phthaloylacridone, and the condensation of the cyanun'cchloride with the 2-amino-3:4-phthaloylacridone to form the compound ofthe Formula 2, and the further condensation of this compound with thetrifluoromethylaniline require much morerrigorous conditions, since thethird chlorine atom in the triazine radical is relatively difficult toexchange. Thus, the reaction is advantageously carried out in ahigh-boiling solvent, for example, in nitrobenzene,ortho-dichlorobenzene, naphthalene or more especially in phenol. Thereaction is advantageously carried out at a temperature above C. Theexchange of the third halogen atom in the triazine ring can also befacilitated by the addition of small amounts of an aromatic sulfonicacid such as benzene sulfonic acid, para-toluene sulfonic acid or moreespecially meta-nitrobenzene sulfonic acid. l

. The products obtained by the process of the invention are suitable fordyeing or printing a very Wide variety of materials, especially for thedyeing or printing of fibers made of natural or regenerated cellulose.The dyestuffs of the invention dye cellulose fibers in valuable reddishblue tints, which tints can be shaded substantially purer with red andviolet. The dyeings obtained therewith are distinguished by a goodfastness to light and good properties of wet fastness and moreespecially are fast to soda boiling, chlorine and chlorite. The newdyestuffs can also be used as pigments. 1

Unless otherwise stated, the parts and percentages in the followingexamples are by weight:

Example 1 A solution of 18.4 parts of cyanuric chloride in parts byvolume of acetone was run into 80 parts by volume of water at 10 to 15C., while stirring well, cyanuric chloride being precipitated in afinely divided form. 19.5 parts of 2:chloro-5-trifiuorornethylanilinewere then added dropwise and 8.4 parts of sodium bicarbonate weresprinkled in during the course of about minutes to adjust the pH valueto 6.8 to 7.1. The reaction mixture was stirred for about '20 minutes at10 to C. until the cyanuric chloride disappeared. The 2-(2'-chloro 5'trifluoromethylphenyl)-amino-4:6-dichloro-1z3z5-triazine so formed wasfiltered ofi, washed with water and then dried in vacuo at to C. The 7yield was 31.4 parts and the product melted at 154 to 155 C.(corrected). When recrystallized from ligroin it melted at 156 C.(corrected).f

,A mixture of 5.1 parts of 2-amino-3;4-phthaloylacridone, 2.6 parts ofthe2-(2-chloro-5-trifiuoromethylphenyl)-amino-4:6-dichloro-1z3:5-triazineobtained as described in the first paragraph, 4 parts by volume of a 2to 4% solution of metanitrobenzene sulfonic acid in nitrobenzene and 46parts by volume of nitrobenzene was stirred for 17 hours at to C. andthen for 4 hours at to C. After cooling the reaction mixture, thedyestutf was filtered olf, washed with alcohol, and then dried. It dyedcotton from a ruby-red vat blue tints fast to wet processing and lightwhen applied by the usual vat dyeing methods. Yield 6.2 parts. Found:Cl, 3.74%; F, 6.08%. Calculated: Cl, 3.73%; F, 5.99%.

By using in accordance with paragraph 1, an equimolecular' proportion of2-(meta-trifiuoromethylphenyl)- amino-4: 6-dich1oro-1 3 S-triazine or 2-[3' 5 -di-(trifiuo- Example 2 A mixture of 5.6 parts of2-amino-7-chloro-3z4- phthaloylacridone, 2.6 parts of 2-(2'-chloro-5'trifluorornethyl-phenyl)-amino 4:6 dichloro-l 3:5-triazine, 0.12 part ofmeta-nitrobenzene sulfonic acid and 46 parts by volume of nitrobenzenewas stirred for 18 hours at 130 to 135 C. and then for 5 hours at to C.The dyestuff, which precipitated in the form of small blue needles, wasfiltered oil at 100 C., washed with alcohol and then dried. Yield: 6:4parts, found: Cl, 10.8%. The dyestuif dyed cotton from a violet vat bluetints fast to soda boiling and light.

A dyestuff with a somewhat more greenish tint was obtained when, in theprocess described in the firstparagraph of Example 2, the2-(2'-chloro-5'-trifluoromethylphenyl) -amino-4 6-dichloro-1 3 2S-triazine was replaced by an equimolecular proportion of2-(3'trifiuoromethy1- phenyl) -amino-4 6-dichloro-1 3 :S-triazine.

Example 3.

A mixture of 20.4 parts of 2-amin0-3:4-phthaloylacridone, 5.4 parts ofcyanuric chloride and 300 parts by volume of nitrobenzene were stirredfor 2 hours at 110 to 115 C, then for 1 hour at 130 to 135 C. and againfor 3 hours at 170 to 180 C. The dyestuif was filtered off at 100 C.,washed with alcohol and then dried. It contained 4.26% of chlorine and12% of nitrogen.

A mixture of 3.85 parts of the dyestufi obtained in the manner describedin the first paragraph of Example 3 and 40 parts by volume ofmeta-trifiuoromethylaniline was stirredfor 3 hours at l50'to C. and thenfor 3 hours at to C. The dyestuff was filtered on at 80 C.,

4 washed with alcohol and then dried. It exhibited dyeing propertiesvery similar to those of the dyestuff obtained from 2-(meta-trifiuoromethylphenyl) -amino-4 6-dichloro- 1:3:5-triazine asdescribed in Example 1. 0

Example 4 A mixture of 6 parts of the product obtained as described inthe first paragraph of Example 3, 12 parts of3:S-di-(trifluoromethyl)-aniline and 75 parts of phenol Were stirred for20 hours at 170 to C. After dilution with 50 parts by volume ofnitrobenzene, the dyestuff was filtered off, washed with alcohol andthen dried. It contained 11.9% of fluorine. The dyestutf so obtaineddyed cotton blue tints possessing an excellent fastness to soda boiling.V i

By replacing in this example, the 3:5-di-(trifluoromethyD-aniline by thesame amount of metal-trifluorornethylaniline,'a dyestuff yielding a moregreenish tint was obtained; 7 I, I

What is claimed is:

1. An anthraquinon'e vat 'dyestuif of the formula in which X and Z eachrepresents a member selected from 50 the group consisting of hydrogenand chlorine, and Y a member selected from the group consisting ofhydrogen and trifluoromethyl.

2. The vat dyestufi of the formula V 3,164,592 e l 5 e 1 a 3. The vatdyestufl? of theforr nula 4. The vat dyestuff of the formula u 0 I E NReferences Cited in the file of this patent UNITED STATES PATENTS 71,719,792 Ackermann et a1 July 2, 1929 2,666,052 Williams et a1 Jan. 12,1954 2,951,842 Ebel et a1. Sept. 6, 1960 OTHER REFERENCES Venkataraman:The Chemistry of Synthetic Dyes, Academic Press, Inc., N.Y., 1952, pp.473, 916, 925 and 1221,

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA